Industrial processes BASF process

The industrial-scale BASF process is characterized by low raw material costs, high conversion and yield, and a simple work-up (Figure 1). 

The oxidative dehydrogenation of methanol to formaldehyde was choosen as model reaction by BASF for performance evaluation of micro reactors [1, 49-51, 108]. In the industrial process a methanol-air mixture of equimolecular ratio of methanol and oxygen is guided through a shallow catalyst bed of silver at 150 °C feed temperature, 600-650 °C exit temperature, atmospheric pressure and a contact time of 10 ms or less. Conversion amounts to 60-70% at a selectivity of about 90%. 

Figure 3.48 Product spectra obtained by measurements of BASF and Rh6ne-Poulenc compared with results of an industrial process. The data given are vol.-% of the product mixture [2],...

Let us recall that by the sol-gel method one can obtain very efficiently very well-defined systems such as Ti silicalite, which can be considered as a single site system where titanium is tetracoordinated in a zeolitic matrix and undergoes epoxidation of propylene or hydroxylahon of benzene to phenol. Bear in mind that it took industry more than 20 years to realize such an industrial processes (Dow-BASF process) [1]). 

An industrial process to produce methanol from carbon monoxide and hydrogen was developed by BASF in 1923 using a zinc oxide-chromia catalyst.361 362 Since this catalyst exhibited relatively low specific activity, high temperature was required. The low equilibrium methanol concentration at this high temperature was compensated by using high pressures. This so-called high-pressure process was operated typically at 200 atm and 350°C. The development of the process and early results on methanol synthesis were reviewed by Natta 363... 

The industrial catalytic Reppe process is usually applied in the production of acrylic acid. The catalyst is NiBr2 promoted by copper halides used under forcing conditions. The BASF process, for example, is operated at 225°C and 100 atm in tetrahydrofuran solvent.188 Careful control of reaction conditions is required to avoid the formation of propionic acid, the main byproduct, which is difficult to separate. Small amounts of acetaldehyde are also formed. Acrylates can be produced by the stoichiometric process [Eq. (7.20)], which is run under milder conditions (30-50°C, 1-7 atm). The byproduct NiCl2 is recycled ... 

As mentioned in the previous section, the carbonylation of methanol to acetic acid is an important industrial process. Whereas the [Co2(CO)s]-catalyzed, iodide-promoted reaction developed by BASF requires pressures of the order of 50 MPa, the Monsanto rhodium-catalyzed synthesis, which is also iodide promoted and which was discovered by Roth and co-workers, can be operated even at normal pressure, though somewhat higher pressures are used in the production units.4,1-413 The rhodium-catalyzed process gives a methanol conversion to acetic acid of 99%, against 90% for the cobalt reaction. The mechanism of the Monsanto process has been studied by Forster.414 The anionic complex m-[RhI2(CO)2]- (95) initiates the catalytic cycle, which is shown in Scheme 26. 

If defined amounts of water are added to the electrolyte, the anodic acetoxylation yields the corresponding aldehydes with very good selectivities. The reaction passes smoothly through the benzyl acetate stage. On the basis of this method, BASF has developed industrial processes for the production of aromatic aldehydes 174-,75>. 

Experiments performed with the reactor, in that case made of titanium, by Worz at BASF in a proprietary reaction revealed 60% yield for the desired product at residence times as low as 40 ms in the micro reactor. This performance was superior to that of the experiments performed in an aluminum capillary, which corresponds well with the reactor design of the industrial process (Figure 3.24). A 2000% gain in space-time yield was found for the porous coated micro structures compared with the aluminum capillaries. 

Ethylenimine can be made from MEA. BASF and Hoechst developed an industrial process that has two steps. 

In this chapter we discuss the mechanistic and other details of a few industrial carbonylation processes. These are carbonylation of methanol to acetic acid, methyl acetate to acetic anhydride, propyne to methyl methacrylate, and benzyl chloride to phenyl acetic acid. Both Monsanto and BASF manufacture acetic acid by methanol carbonylation, Reaction 4.1. The BASF process is older than the Monsanto process. The catalysts and the reaction conditions for the two processes are also different and are compared in the next section. Carbonylation of methyl acetate to acetic anhydride, according to reaction 4.2, is a successful industrial process that has been developed by Eastman Kodak. The carbonylation of propyne (methyl acetylene) in methanol to give methyl methacrylate has recently been commercialized by Shell. The Montedison carbonylation process for the manufacture of phenyl acetic acid from benzyl chloride is noteworthy for the clever combination of phase-transfer and organometallic catalyses. Hoechst has recently reported a novel carbonylation process for the drug ibuprofen. 

Hundreds of impressive examples of enantioselective lipase-catalysed reactions are known, including industrial processes as in the case of the BASF method of chiral amine production (Collins et al. 1997 Breuer et al. 2004 Schmid and Verger 1998). However, the classical problem of substrate acceptance or lack of enantioselectivity (or both) persists. We were able to meet this challenge in model studies regarding the hydrolytic kinetic resolution of the ester rac-1 with formation of carboxylic acid 2, catalysed by the lipase from Pseudomonas aeruginosa. The wild-type (WT) lipase is only slightly (S )-selective, the selectivity factor amounting to a mere E = 1.1 (Scheme 1). 

This technique ssentially industrialized by BASF, remained economically competitive until the advent of the so-called third-generation adiabatic processes emplo>ing highly selective catalysts. The operating conditions and average performance of this type of dehydrogenation are as follows ... 

As far as large ale industrial application is concerned, the major Reppepropionic acid from ethylene. This was carried out by a BASF process (plant of about 30000 l/a) under 240 atm at 2 0 C with NKCO) as the catalyst. It also appears that Monsanto has a rhodium-catalyzed process on stream, which operates under milder conditions. 

The industrial process for propene oxide manufacture is commonly referred to as the HPPO (hydrogen peroxide propene oxide) process. EniChem set up a prototype plant in 2002 [150]. BASF/Dow Chemicals and Degussa, in turn, have the construction of commercial plants already in progress or at the planning stage [151]. 

Several multi-ton industrial processes still use enzymatic resolution, often with lipases that tolerate different substrates. BASF, for example, makes a range of chiral amines by acylating racemic amines with proprietary esters. Only one enantiomer is acylated to an amide, which can be readily separated from the unreacted amine. Many fine chemicals producers also employ acylases and amidases to resolve chiral amino acids on a large scale. l-Acylases, for example, can resolve acyl d,l-amino acids by producing the I-amino acids and leaving the N-acyl-l-amino acid untouched after separation, the latter can be racemized and returned to the reaction. d-Acylase forms the alternative product. Likewise, DSM and others have an amidase process that works on the same principle d,l-amino acid amides are selectively hydrolyzed, and the remaining d-amino acid amide can be either racemized or chemically hydrolyzed. 

Value added products, such as the reduction of oxalic acid to glyoxylic acid, are nowadays developed at an industrial scale (BASF—Badische Anilin und Soda-Fabriken). This process uses non-precious metals such as lead. This electrode material reduces carbon dioxide to formic acid in an aqueous medium and to oxalic acid in an organic solvent. This approach can be used to develop environmentally friendly value added products from abundant anthropogenic carbon dioxide. 

Lutensol . [BASF AG] Detergent, wetting agent, dispersant, emulsifier for household and industrial detergents, chemical processing, leather, fur, paper, paint and dye industries. 

If you think these rearrangements sound like academic reactions and too refined for the rough and tumble of industry, you re in for a surprise. The Carroll rearrangement, a [3,3) sigmatropic shift, is an important industrial process used to make vitamin A and some perfumery and flavouring compounds at BASF in Germany. 

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